CN109319806A - A kind of method of the integral formula SSZ-13 molecular sieve of mixed templates dry glue - Google Patents
A kind of method of the integral formula SSZ-13 molecular sieve of mixed templates dry glue Download PDFInfo
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/026—After-treatment
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- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
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- Y02P20/50—Improvements relating to the production of bulk chemicals
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- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Abstract
The invention discloses a kind of methods of the integral formula SSZ-13 molecular sieve of mixed templates dry glue.Mixed templates use based on choline chloride in this method, with N, N, N- trimethyl adamantane ammonium, mixed templates are mediated with raw material in proportion and squeeze preforming, then crystallization under certain temperature, obtained SSZ-13 molecular sieve have that purity is high, crystal phase be pure, even grain size in autoclave by immobilized ph gradient strip, compared with the accumulation aperture of concentration, biggish specific surface area and suitable acidic site.The SSZ-13 molecular sieve thermal stability of the method for the present invention synthesis is high, has the accumulation hole relatively concentrated near 4nm, and have very good catalytic effect in the catalysis of MTO methanol-to-olefins reaction.Monoblock type dry glue synthesis process can reduce the dust pollution and wastage of material when the processing of cost powder compared with hydrothermal synthesis, traditional dry glue and solid-phase sequencing, at low cost, water consumption is few, and preparation process is simple to operation, and binder free adds, the features such as active site exposure, catalytic effect is strong.
Description
Technical field
The invention belongs to catalyst carrier preparation fields, and in particular to the synthetic method of monoblock type SSZ-13 molecular sieve.
Background technique
SSZ-13 molecular sieve is the CHA structure with the big cage of chabasie aperture, by AlO4And SiO4Tetrahedron passes through oxygen atom
It is end to end, it is arranged in elliposoidal (0.73nm × 1.2nm) crystal with octatomic ring structure, and all three-dimensional friendships in an orderly manner
The size in entry road is the small pore molecular sieve of 0.38nm × 0.38nm.The molecular sieve is medium strong due to its regular cellular structure
The Acidity of degree has excellent catalytic properties preparing low carbon olefinic hydrocarbon with methanol (MTO) reaction.
The 80s and 90s in 20th century, Zones utilize hydro-thermal method for the first time, and with N, N, N- trimethyl adamantane ammonium is template,
Successfully synthesize the SSZ-13 molecular sieve (US No.4,544,538) of high-purity.In decades, although there is Many researchers successive
Using tetraethyl ammonium hydroxide [ZONES S I.Preparation of zeolite SSZ-13:US8007763B2 [P]
.2011-08-30.], benzyltrimethylammon.um [WU L L.Dual template synthesis of highly
mesoporous SSZ-13 zeolite with improved stability in the methanol-to-olefins
Reaction [J] .Catal.Commun., 2012,48:9492-9494.], high molecular quaternary [WU L L.Mesoporous
SSZ-13 zeolite prepared by a dual-template method with improved performance
In the methanol-to-olefins reaction [J] .J.Catal., 2013,289:27-40.] and triethylamine [Korea Spro
Research [J] inorganic chemicals industry of beautiful hybrid template method low cost synthesis SSZ-13 molecular sieve, 2016,48 (9): 36-39.] etc.
Amine (ammonium) class part replaces N, N, N- trimethyl adamantane ammonium, but is all built upon on hydro-thermal method synthetic method.
104709917 A of CN discloses a kind of method for synthesizing SSZ-13 molecular sieve by solid-phase grinding, is ground by solid phase
The method of SSZ-13 molecular sieve is merged into comprising steps of weighing silicon source, silicon source, alkali source, template progress crystallization, has been reacted
Crystallization product is obtained after, cooling washing is dried to obtain molecular screen primary powder, then by molecular screen primary powder at 550 DEG C to neutrality
5 hours are roasted in air to get final products SSZ-13 molecular sieve is arrived.But the powder SSZ-13 molecular sieve that this method obtains is pure
Spend lower, accumulation pore size dispersion is uneven, and single aperture centrality is poor, and synthesizes key reaction object used in template
N, N- dimethyl cyclohexyl amine are irritant to respiratory mucosa, the risk such as inflammable.
CN106745034A discloses a kind of method and its application of double template one-step synthesis SSZ-13 molecular sieve.The party
Method uses N, N, and N- trimethyl adamantane ammonium and choline chloride are synthesized as double template through hydro-thermal method, and loads upper Cu2+Afterwards,
(NH is post-processed applied to diesel vehicle3- SCR) NO in system catalystxElimination process.Although the method has been also applied to chlorination
Choline still uses hydrothermal synthesis method as auxiliary template agent, and template dosage is still higher, and after crystallization purity compared with
Low, yield is relatively low.
CN107115888A discloses a kind of preparation method of high silicon CHA type SSZ-13 molecular screen membrane, and this method is using more
Template combination prepares high performance SSZ-13 molecular screen membrane in porous ceramic support, and step is that will be coated with SSZ-13 molecular sieve
The porous ceramics tubulose supporter outer wall of crystal seed, density requirements are in 0.2-2mg/cm2, it is immersed in the reaction solution of thermal and hydric environment
In, crystallization is carried out in stainless steel autoclave, and SSZ-13 molecular screen membrane is made.This method technique to seed coating layer require compared with
Height, technical process are complex.
In general, conventional hydrothermal synthesis, Dry gel conversion method and solid-phase grinding [JIN Y Y, Solvent-free
Synthesis of silicoalumin ophosphate zeolites [J] .Angew Chem.&Int.Ed., 2013,52
(35): 9172-9175.] synthesize finally obtained product be all it is powdered, when industrial application, must add a certain amount of adhesive
Molding.And the processing and processing of powder sample easily cause dust pollution and product to waste, and adhesive is added when molding and is possible to
Duct, or the active sites of covering molecular sieve are blocked, cause catalytic efficiency to reduce, the SSZ-13 molecular sieve of monoblock type crystallization forming is so far
There is not patent report until the present.By the monoblock type SSZ- of a variety of mixed templates dry glue synthesis shown in the method
13 molecular sieves have extraordinary aperture structure and physicochemical property, can pass through Cu2+Or other ion exchanges, more born
Carry the SSZ-13 molecular sieve catalyst of metal species.
Summary of the invention
The problem to be solved in the present invention is to provide a kind of low cost, simple process, more environmentally-friendly hybrid template dry glues
The method of integral formula SSZ-13 molecular sieve.
The present invention realizes that above-mentioned target adopts the following technical scheme that and is achieved:
The present invention provides a kind of method of integral formula SSZ-13 molecular sieve of mixed templates dry glue, including following step
It is rapid:
1) by silicon source, silicon source and sodium source, mixed grinding is uniform, and control each element molar ratio is 1SiO2: 0.1-
0.02Al2O3:0.01-0.06Na2O；
2) at room temperature, by water, N, N, two kinds of templates of N- trimethyl adamantane ammonium and choline chloride are according to molar ratio ratio
Example 2-15H2O:0.005-0.05R1:0.01-0.30R2It is added sequentially in beaker；
3) solution after mixing evenly is added in the uniform solid material of grinding, using kneader, after sufficiently mediating,
Extrusion forming obtains raw material immobilized ph gradient strip；
4) it by molding raw material immobilized ph gradient strip, is put into polytetrafluoroethylene (PTFE) pallet, is placed in the polytetrafluoroethylene (PTFE) of a small amount of water
In liner autoclave, after sealing, 1~3d of crystallization at 155 DEG C -165 DEG C；
5) after being cooled to room temperature reaction kettle, through deionized water washing, drying；
6) use mass fraction 30%-50% ammonium sulfate, in 80 DEG C -90 DEG C of progress ion exchange 8 hours, after draining
120 drying, roast 4 hours at 500 DEG C -600 DEG C, obtain monoblock type SSZ-13 molecular sieve；
Wherein reaction mass sodium source is with Na2O meter, silicon source are with Al2O3Meter, silicon source are with SiO2Meter, solvent are with H2O meter, template
N, N, N- trimethyl adamantane ammonium are with R1Meter, template choline chloride is with R2Meter, each reaction mass is according to molar ratio are as follows: 1SiO2:
0.1-0.02Al2O3:0.01-0.06Na2O:2-15H2O:0.005-0.05R1:0.01-0.30R2It feeds intake, wherein R1For N,
N, N- trimethyl adamantane ammonium, R2For choline chloride.
In above-mentioned technical proposal, the silicon source is preferably white carbon black, silicon powder or sodium metasilicate, silicon source be preferably sodium metaaluminate,
Aluminum sulfate or aluminium hydroxide, sodium source are preferably sodium metaaluminate or sodium hydroxide.
The present invention also provides a kind of monoblock type SSZ-13 molecular sieves that the above method is prepared in methanol oxidation alkene
Application in hydrocarbon.
Compared with prior art, the beneficial effects of the present invention are:
Under conditions of the present invention is preformed in few solvent by raw material, high-crystallinity is obtained, pure phase and crystallite dimension is equal
Even SSZ-13 molecular sieve, it is possible to reduce the yield loss in hydrothermal synthesis method in last handling process, yield are significantly larger than water
Thermal method synthesis, reduces the use of aqueous solvent to the maximum extent.The side of Dry gel conversion method crystallization after the present invention uses raw material preforming
Method greatly simplifies the technical process of molecular sieve conventional hydrothermal method synthetic powder reshaping, reduces powder sample and formed
Dust pollution and product waste caused by journey avoid the adhesive blocking duct being added when molding, or covering molecular sieve
Active sites, improve the catalytic efficiency of SSZ-13 molecular sieve catalyst；Meanwhile the preforming dry gel conversion method of raw material is not only compared with water
Thermal method reduces expensive template N, N, the dosage of N- trimethyl adamantane ammonium, also using new template agent choline chloride instead of big
Part N, N, N- trimethyl adamantane ammonium, greatly reduce production cost and the pollution to environment, there is huge industrial application
Prospect.In short, the SSZ-13 molecular sieve thermal stability of the method for the present invention synthesis is high, there is the accumulation hole relatively concentrated near 4nm, and
There is very good catalytic effect in the catalysis reaction of MTO methanol-to-olefins.Monoblock type dry glue synthesis process and hydrothermal synthesis,
Traditional dry glue is compared with solid-phase sequencing, can reduce dust pollution and wastage of material when the processing of cost powder, at low cost, is used
The features such as water is few, and preparation process is simple to operation, and binder free adds, active site exposure, catalytic effect is strong.
Detailed description of the invention
Fig. 1 is the XRD spectra of the monoblock type SSZ-13 molecular sieve of 1 mixed templates dry glue of embodiment of the present invention synthesis；
Fig. 2 is the scanning electron microscope (SEM) photograph of the monoblock type SSZ-13 molecular sieve of 1 mixed templates dry glue of embodiment of the present invention synthesis；
Fig. 3 is the N of the monoblock type SSZ-13 molecular sieve of 1 mixed templates dry glue of embodiment of the present invention synthesis2Adsorption desorption etc.
Warm curve and graph of pore diameter distribution；
Fig. 4 is the NH of the monoblock type SSZ-13 molecular sieve of 1 mixed templates dry glue of embodiment of the present invention synthesis3- TPD inhales de-
Attached drawing；
Fig. 5 is the temperature programming XRD of the monoblock type SSZ-13 molecular sieve of 1 mixed templates dry glue of embodiment of the present invention synthesis
Figure；
Fig. 6 is the monoblock type SSZ-13 molecular sieve of 1-12 of embodiment of the present invention mixed templates dry glue synthesis in methanol alkene
The effect picture of the catalytic conversion of methanol in hydrocarbon；
Fig. 7 is that the SSZ-13 molecular sieve that the embodiment of the present invention 1 is synthesized with comparative example hydro-thermal method is applied in methanol-to-olefins
The catalytic conversion effect picture of methanol.
Specific embodiment
With reference to the accompanying drawing and specific embodiment is described in further detail technical solution of the present invention and technical effect:
The following examples can make the professional technician of this profession that the present invention be more fully understood, but not with any side
The formula limitation present invention.
Embodiment 1
(1) at room temperature by 188g white carbon black, the mixing of 25g sodium metaaluminate is fully ground；
(2) at room temperature, the water of 263g, the N of 150g, N are sequentially added in small beaker, N- trimethyl adamantane ammonium (contains
25%) and 50g choline chloride for amount, to be evenly stirred until choline chloride in N, N is completely molten in N- trimethyl adamantane ammonium salt solution
Solution；
(3) solution being transparent will be completely dissolved to be added in the uniform solid material of grinding, using kneader, sufficiently
It mediates 2 hours, with cylindrical extrusion sheet metal forming；
(4) it by molding raw material immobilized ph gradient strip, is put into polytetrafluoroethylene (PTFE) pallet, is placed in the polytetrafluoroethylene (PTFE) of a small amount of water
In liner autoclave, after sealing, the crystallization 2d at 160 DEG C obtains Na-SSZ-13 molecular sieve；
(5) after being cooled to room temperature reaction kettle, through deionized water washing, drying；
(6) use mass fraction 30% ammonium sulfate, in 80 DEG C progress ion exchange 8 hours, obtain NH3-SSZ-13
Molecular sieve, 120 DEG C of drying after draining, roasts 4 hours at 600 DEG C, obtains monoblock type SSZ-13 molecular sieve.
The stoicheiometry of the system is as follows: SiO2: Al2O3: Na2O:H2O:R1: R2For 1:0.035:0.039:7.227:
0.031:0.122.
Basic performance detection
After the monoblock type SZ-13 sieve sample crystallization of the preforming synthesis of 1 dry glue of embodiment, test XRD inspection is carried out
Survey (Fig. 1), SEM detects (Fig. 2), NH3- TPD detects (Fig. 3), N2Adsorption desorption isothermal curve and pore-size distribution (Fig. 4), high-temp in-situ
XRD detect (Fig. 5), different silica alumina ratio methanol-to-olefins catalytic conversion detection (Fig. 6) and the preforming SSZ-13 of dry glue divide
Son sieve and the catalytic conversion of the methanol-to-olefins of hydrothermal synthesis SSZ-13 molecular sieve compare (Fig. 7).
From Fig. 1 middle skeleton structure as it can be seen that there is the characteristic peak of SSZ-13 molecular sieve, and baseline is more smooth and without stray crystal diffraction
Peak illustrates that crystal effect is preferable, and free from admixture.
From the microcosmic appearance shape result of Fig. 2 as it can be seen that the SSZ-13 molecular sieve showed in figure is the aggregation of blocky-shaped particle,
Interlaced accumulation between grain, production die size is relatively uniform, and about 0.5~1 μm.
After the monoblock type SZ-13 sieve sample of the preforming synthesis of 1 dry glue of embodiment is carried out ion exchange and is roasted,
Carry out N2Adsorption desorption isothermal curve and graph of pore diameter distribution.It can be seen that monoblock type SSZ-13 molecular sieve from the graph of pore diameter distribution of Fig. 3
Crystal has near 4nm compared with the accumulation hole concentrated, and in obtained related data, specific surface area offers report with respect to conventional hydrothermal French
Road volume related data is slightly higher, and large specific surface area, aperture is moderate, is more advantageous to the progress of catalysis reaction.
After the monoblock type SZ-13 sieve sample of the preforming synthesis of 1 dry glue of embodiment is carried out ion exchange and is roasted,
Carry out NH3The analysis detection of-TPD.NH in Fig. 43The analysis detection of-TPD the results show that such molecular sieve SSZ-13 faintly acid
Site is relatively concentrated, and its strong acid site range is larger, and such catalyst has good catalytic performance to alcohol alkene.
High-temperature stability point will be carried out after the monoblock type SZ-13 sieve sample crystallization of the preforming synthesis of 1 dry glue of embodiment
Analysis, from in-situ high temperature XRD spectrogram under Fig. 5 air atmosphere as it can be seen that the diffraction maximum of framework of molecular sieve is complete after 800 DEG C of high temperature are burnt
It is good, it does not collapse, illustrates that the catalyst has excellent thermal stability.
Catalytic conversion performance test
SSZ-13 molecular sieve immobilized ph gradient strip after roasting is truncated into the segment of 5mm, weighs 400g, fixed bed activity is put into and comments
In valence device, 450 DEG C of reaction temperature；M (methanol): m (water)=40:60；Methanol quality air speed is 3.75h-1。
The catalytic conversion figure at any time that SSZ-13 molecular sieve is reacted in methanol oxidation propylene is as shown in Figure 6.
By experiment detection discovery, the SSZ-13 molecular sieve synthesized using the embodiment 2-12 of the method for the present invention,
Its XRD detection, SEM detection, N2Adsorption desorption, NH3- TPD, in-situ high temperature XRD figure result obtain similar conclusion, therefore, hereafter
It repeats no more, no longer provides structured testing figure one by one.Only catalyzed conversion performance is carried out to the product being prepared to test.
Embodiment 2
(1) 188g white carbon black, 18g anhydrous slufuric acid aluminium and the mixing of 23g sodium metaaluminate are fully ground at room temperature；
(2) at room temperature, the water of 263g, the N of 150g, N are sequentially added in small beaker, N- trimethyl adamantane ammonium (contains
25%) and 50g choline chloride for amount, to be evenly stirred until choline chloride in N, N is completely molten in N- trimethyl adamantane ammonium salt solution
Solution；
(3) solution being transparent will be completely dissolved to be added in the uniform solid material of grinding, using kneader, sufficiently
It mediates 2 hours, with cylindrical extrusion sheet metal forming；
(4) it by molding raw material immobilized ph gradient strip, is put into polytetrafluoroethylene (PTFE) pallet, is placed in the polytetrafluoroethylene (PTFE) of a small amount of water
In liner autoclave, after sealing, the crystallization 2d at 160 DEG C obtains Na-SSZ-13 molecular sieve；
(5) after being cooled to room temperature reaction kettle, through deionized water washing, drying；
(6) use mass fraction 30% ammonium sulfate, in 80 DEG C progress ion exchange 8 hours, obtain NH3-SSZ-13
Molecular sieve, 120 DEG C of drying after draining, roasts 4 hours at 600 DEG C, obtains monoblock type SSZ-13 molecular sieve.
The stoicheiometry of the system is as follows: SiO2: Al2O3: Na2O:H2O:R1: R2For 1:0.050:0.036:7.227:
0.031:0.122.
For catalytic conversion performance test methods with embodiment 1, test result is shown in Fig. 6.
Embodiment 3
(1) 188g white carbon black, 50g anhydrous slufuric acid aluminium and the mixing of 23g sodium metaaluminate are fully ground at room temperature；
(2) at room temperature, the water of 263g, the N of 150g, N are sequentially added in small beaker, N- trimethyl adamantane ammonium (contains
25%) and 50g choline chloride for amount, to be evenly stirred until choline chloride in N, N is completely molten in N- trimethyl adamantane ammonium salt solution
Solution；
(3) solution being transparent will be completely dissolved to be added in the uniform solid material of grinding, using kneader, sufficiently
It mediates 2 hours, with cylindrical extrusion sheet metal forming；
(4) it by molding raw material immobilized ph gradient strip, is put into polytetrafluoroethylene (PTFE) pallet, is placed in the polytetrafluoroethylene (PTFE) of a small amount of water
In liner autoclave, after sealing, the crystallization 2d at 160 DEG C obtains Na-SSZ-13 molecular sieve；
(5) after being cooled to room temperature reaction kettle, through deionized water washing, drying；
(6) use mass fraction 30% ammonium sulfate, in 80 DEG C progress ion exchange 8 hours, obtain NH3-SSZ-13
Molecular sieve, 120 DEG C of drying after draining, roasts 4 hours at 600 DEG C, obtains monoblock type SSZ-13 molecular sieve.
The stoicheiometry of the system is as follows: SiO2: Al2O3: Na2O:H2O:R1: R2For 1:0.083:0.036:7.227:
0.031:0.122.
For catalytic conversion performance test methods with embodiment 1, test result is shown in Fig. 6.
Embodiment 4
(1) 188g white carbon black, 35g anhydrous slufuric acid aluminium and the mixing of 7g sodium hydroxide are fully ground at room temperature；
(2) at room temperature, the water of 263g, the N of 150g, N are sequentially added in small beaker, N- trimethyl adamantane ammonium (contains
25%) and 50g choline chloride for amount, to be evenly stirred until choline chloride in N, N is completely molten in N- trimethyl adamantane ammonium salt solution
Solution；
(3) solution being transparent will be completely dissolved to be added in the uniform solid material of grinding, using kneader, sufficiently
It mediates 2 hours, with cylindrical extrusion sheet metal forming；
(4) it by molding raw material immobilized ph gradient strip, is put into polytetrafluoroethylene (PTFE) pallet, is placed in the polytetrafluoroethylene (PTFE) of a small amount of water
In liner autoclave, after sealing, the crystallization 2d at 160 DEG C obtains Na-SSZ-13 molecular sieve；
(5) after being cooled to room temperature reaction kettle, through deionized water washing, drying；
(6) use mass fraction 30% ammonium sulfate, in 80 DEG C progress ion exchange 8 hours, obtain NH3-SSZ-13
Molecular sieve, 120 DEG C of drying after draining, roasts 4 hours at 600 DEG C, obtains monoblock type SSZ-13 molecular sieve.
The stoicheiometry of the system is as follows: SiO2: Al2O3: Na2O:H2O:R1: R2For 1:0.035:0.030:7.227:
0.031:0.122.
For catalytic conversion performance test methods with embodiment 1, test result is shown in Fig. 6.
Embodiment 5
(1) 188g white carbon black and 23g sodium metaaluminate are mixed at room temperature and is fully ground；
(2) at room temperature, the water of 263g, the N of 150g, N are sequentially added in small beaker, N- trimethyl adamantane ammonium (contains
25%) and 50g choline chloride for amount, to be evenly stirred until choline chloride in N, N is completely molten in N- trimethyl adamantane ammonium salt solution
Solution；
(3) solution being transparent will be completely dissolved to be added in the uniform solid material of grinding, using kneader, sufficiently
It mediates 2 hours, with cylindrical extrusion sheet metal forming；
(4) it by molding raw material immobilized ph gradient strip, is put into polytetrafluoroethylene (PTFE) pallet, is placed in the polytetrafluoroethylene (PTFE) of a small amount of water
In liner autoclave, after sealing, the crystallization 2d at 160 DEG C obtains Na-SSZ-13 molecular sieve；
(5) after being cooled to room temperature reaction kettle, through deionized water washing, drying；
(6) use mass fraction 30% ammonium sulfate, in 80 DEG C progress ion exchange 8 hours, obtain NH3-SSZ-13
Molecular sieve, 120 DEG C of drying after draining, roasts 4 hours at 600 DEG C, obtains monoblock type SSZ-13 molecular sieve.
The stoicheiometry of the system is as follows: SiO2: Al2O3: Na2O:H2O:R1: R2For 1:0.032:0.036:7.227:
0.031:0.122.
For catalytic conversion performance test methods with embodiment 1, test result is shown in Fig. 6.
Embodiment 6
(1) 188g white carbon black, 25g sodium metaaluminate and the mixing of 2g sodium hydroxide are fully ground at room temperature；
(2) at room temperature, the water of 263g, the N of 150g, N are sequentially added in small beaker, N- trimethyl adamantane ammonium (contains
25%) and 50g choline chloride for amount, to be evenly stirred until choline chloride in N, N is completely molten in N- trimethyl adamantane ammonium salt solution
Solution；
(3) solution being transparent will be completely dissolved to be added in the uniform solid material of grinding, using kneader, sufficiently
It mediates 2 hours, with cylindrical extrusion sheet metal forming；
(4) it by molding raw material immobilized ph gradient strip, is put into polytetrafluoroethylene (PTFE) pallet, is placed in the polytetrafluoroethylene (PTFE) of a small amount of water
In liner autoclave, after sealing, the crystallization 2d at 160 DEG C obtains Na-SSZ-13 molecular sieve；
(5) after being cooled to room temperature reaction kettle, through deionized water washing, drying；
(6) use mass fraction 30% ammonium sulfate, in 80 DEG C progress ion exchange 8 hours, obtain NH3-SSZ-13
Molecular sieve, 120 DEG C of drying after draining, roasts 4 hours at 600 DEG C, obtains monoblock type SSZ-13 molecular sieve.
The stoicheiometry of the system is as follows: SiO2: Al2O3: Na2O:H2O:R1: R2For 1:0.035:0.048:7.227:
0.031:0.122.
For catalytic conversion performance test methods with embodiment 1, test result is shown in Fig. 6.
Embodiment 7
(1) at room temperature by 188g white carbon black, the mixing of 25g sodium metaaluminate is fully ground；
(2) at room temperature, the water of 300g, the N of 100g, N are sequentially added in small beaker, N- trimethyl adamantane ammonium (contains
25%) and 50g choline chloride for amount, to be evenly stirred until choline chloride in N, N is completely molten in N- trimethyl adamantane ammonium salt solution
Solution；
(3) solution being transparent will be completely dissolved to be added in the uniform solid material of grinding, using kneader, sufficiently
It mediates 2 hours, with cylindrical extrusion sheet metal forming；
(4) it by molding raw material immobilized ph gradient strip, is put into polytetrafluoroethylene (PTFE) pallet, is placed in the polytetrafluoroethylene (PTFE) of a small amount of water
In liner autoclave, after sealing, the crystallization 2d at 160 DEG C obtains Na-SSZ-13 molecular sieve；
(5) after being cooled to room temperature reaction kettle, through deionized water washing, drying；
(6) use mass fraction 30% ammonium sulfate, in 80 DEG C progress ion exchange 8 hours, obtain NH3-SSZ-13
Molecular sieve, 120 DEG C of drying after draining, roasts 4 hours at 600 DEG C, obtains monoblock type SSZ-13 molecular sieve.
The stoicheiometry of the system is as follows: SiO2: Al2O3: Na2O:H2O:R1: R2For 1:0.035:0.039:7.227:
0.021:0.122.
For catalytic conversion performance test methods with embodiment 1, test result is shown in Fig. 6.
Embodiment 8
(1) at room temperature by 188g white carbon black, the mixing of 25g sodium metaaluminate is fully ground；
(2) at room temperature, the water of 330g, the N of 60g, N, N- trimethyl adamantane ammonium (content are sequentially added in small beaker
25%) and 100g choline chloride, to be evenly stirred until choline chloride in N, N is completely dissolved in N- trimethyl adamantane ammonium salt solution；
(3) solution being transparent will be completely dissolved to be added in the uniform solid material of grinding, using kneader, sufficiently
It mediates 2 hours, with cylindrical extrusion sheet metal forming；
(4) it by molding raw material immobilized ph gradient strip, is put into polytetrafluoroethylene (PTFE) pallet, is placed in the polytetrafluoroethylene (PTFE) of a small amount of water
In liner autoclave, after sealing, the crystallization 2d at 160 DEG C obtains Na-SSZ-13 molecular sieve；
(5) after being cooled to room temperature reaction kettle, through deionized water washing, drying；
(6) use mass fraction 30% ammonium sulfate, in 80 DEG C progress ion exchange 8 hours, obtain NH3-SSZ-13
Molecular sieve, 120 DEG C of drying after draining, roasts 4 hours at 600 DEG C, obtains monoblock type SSZ-13 molecular sieve.The chemistry of the system is matched
Than as follows: SiO2: Al2O3: Na2O:H2O:R1: R2For 1:0.035:0.039:7.227:0.012:0.243.
For catalytic conversion performance test methods with embodiment 1, test result is shown in Fig. 6.
Embodiment 9
(1) 188g white carbon black, 25g sodium metaaluminate and the mixing of 27g Aluminium Sulphate usp (powder) are fully ground at room temperature；
(2) at room temperature, the water of 263g, the N of 150g, N are sequentially added in small beaker, N- trimethyl adamantane ammonium (contains
25%) and 50g choline chloride for amount, to be evenly stirred until choline chloride in N, N is completely molten in N- trimethyl adamantane ammonium salt solution
Solution；
(3) solution being transparent will be completely dissolved to be added in the uniform solid material of grinding, using kneader, sufficiently
It mediates 2 hours, with cylindrical extrusion sheet metal forming；
(4) it by molding raw material immobilized ph gradient strip, is put into polytetrafluoroethylene (PTFE) pallet, is placed in the polytetrafluoroethylene (PTFE) of a small amount of water
In liner autoclave, after sealing, the crystallization 2d at 160 DEG C obtains Na-SSZ-13 molecular sieve；
(5) after being cooled to room temperature reaction kettle, through deionized water washing, drying；
(6) use mass fraction 30% ammonium sulfate, in 80 DEG C progress ion exchange 8 hours, obtain NH3-SSZ-13
Molecular sieve, 120 DEG C of drying after draining, roasts 4 hours at 600 DEG C, obtains monoblock type SSZ-13 molecular sieve.
The stoicheiometry of the system is as follows: SiO2: Al2O3: Na2O:H2O:R1: R2For 1:0.062:0.039:7.227:
0.031:0.122.
For catalytic conversion performance test methods with embodiment 1, test result is shown in Fig. 6.
Embodiment 10
(1) 188g white carbon black, 25g sodium metaaluminate and the mixing of 6g Aluminium Sulphate usp (powder) are fully ground at room temperature；
(2) at room temperature, the water of 263g, the N of 150g, N are sequentially added in small beaker, N- trimethyl adamantane ammonium (contains
25%) and 50g choline chloride for amount, to be evenly stirred until choline chloride in N, N is completely molten in N- trimethyl adamantane ammonium salt solution
Solution；
(3) solution being transparent will be completely dissolved to be added in the uniform solid material of grinding, using kneader, sufficiently
It mediates 2 hours, with cylindrical extrusion sheet metal forming；
(4) it by molding raw material immobilized ph gradient strip, is put into polytetrafluoroethylene (PTFE) pallet, is placed in the polytetrafluoroethylene (PTFE) of a small amount of water
In liner autoclave, after sealing, the crystallization 2d at 160 DEG C obtains Na-SSZ-13 molecular sieve；
(5) after being cooled to room temperature reaction kettle, through deionized water washing, drying；
(6) use mass fraction 30% ammonium sulfate, in 80 DEG C progress ion exchange 8 hours, obtain NH3-SSZ-13
Molecular sieve, 120 DEG C of drying after draining, roasts 4 hours at 600 DEG C, obtains monoblock type SSZ-13 molecular sieve.
The stoicheiometry of the system is as follows: SiO2: Al2O3: Na2O:H2O:R1: R2For 1:0.035:0.042:7.227:
0.031:0.122.
For catalytic conversion performance test methods with embodiment 1, test result is shown in Fig. 6.
Embodiment 11
(1) 230g white carbon black, 25g sodium metaaluminate and the mixing of 2g sodium hydroxide are fully ground at room temperature；
(2) at room temperature, the water of 330g, the N of 180g, N are sequentially added in small beaker, N- trimethyl adamantane ammonium (contains
25%) and 65g choline chloride for amount, to be evenly stirred until choline chloride in N, N is completely molten in N- trimethyl adamantane ammonium salt solution
Solution；
(3) solution being transparent will be completely dissolved to be added in the uniform solid material of grinding, using kneader, sufficiently
It mediates 2 hours, with cylindrical extrusion sheet metal forming；
(4) it by molding raw material immobilized ph gradient strip, is put into polytetrafluoroethylene (PTFE) pallet, is placed in the polytetrafluoroethylene (PTFE) of a small amount of water
In liner autoclave, after sealing, the crystallization 2d at 160 DEG C obtains Na-SSZ-13 molecular sieve；
(5) after being cooled to room temperature reaction kettle, through deionized water washing, drying；
(6) use mass fraction 30% ammonium sulfate, in 80 DEG C progress ion exchange 8 hours, obtain NH3-SSZ-13
Molecular sieve, 120 DEG C of drying after draining, roasts 4 hours at 600 DEG C, obtains monoblock type SSZ-13 molecular sieve.
The stoicheiometry of the system is as follows: SiO2: Al2O3: Na2O:H2O:R1: R2For 1:0.031:0.039:7.325:
0.030:0.129.
For catalytic conversion performance test methods with embodiment 1, test result is shown in Fig. 6.
Embodiment 12
(1) 265g white carbon black, 25g sodium metaaluminate and the mixing of 4g sodium hydroxide are fully ground at room temperature；
(2) at room temperature, the water of 370g, the N of 210g, N are sequentially added in small beaker, N- trimethyl adamantane ammonium (contains
25%) and 72g choline chloride for amount, to be evenly stirred until choline chloride in N, N is completely molten in N- trimethyl adamantane ammonium salt solution
Solution；
(3) solution being transparent will be completely dissolved to be added in the uniform solid material of grinding, using kneader, sufficiently
It mediates 2 hours, with cylindrical extrusion sheet metal forming；
(4) it by molding raw material immobilized ph gradient strip, is put into polytetrafluoroethylene (PTFE) pallet, is placed in the polytetrafluoroethylene (PTFE) of a small amount of water
In liner autoclave, after sealing, the crystallization 2d at 160 DEG C obtains Na-SSZ-13 molecular sieve；
(5) after being cooled to room temperature reaction kettle, through deionized water washing, drying；
(6) use mass fraction 30% ammonium sulfate, in 80 DEG C progress ion exchange 8 hours, obtain NH3-SSZ-13
Molecular sieve, 120 DEG C of drying after draining, roasts 4 hours at 600 DEG C, obtains monoblock type SSZ-13 molecular sieve.
The stoicheiometry of the system is as follows: SiO2: Al2O3: Na2O:H2O:R1: R2For 1:0.025:0.040:7.212:
0.030:0.124.
For catalytic conversion performance test methods with embodiment 1, test result is shown in Fig. 6.
Hydro-thermal comparative example
In addition to water in material, rest materials proportion is same as Example 1, and water increases 5-10 times, is formed and hydro-thermal shape
The consistent mixed liquor of state stirs crystallization, crystallization time and temperature and subsequent processing mode and implements in autoclave
Example 1 is identical, the catalyzed conversion of the methanol-to-olefins of obtained hydro-thermal SSZ-13 molecular sieve and the preforming SSZ-13 molecular sieve of dry glue
Rate is shown in Fig. 7.
The Applicant declares that the above is only several case study on implementation in the present invention, not the present invention is done any
Formal limitation, the invention is not limited to above-mentioned method detaileds.Any person skilled in the art is not departing from this
Within the scope of inventive technique scheme, any improvement in the present invention, or using the disclosure above structure or technology contents make it is a little
Change or modification, are considered as equivalent case.It is all to the technology of the present invention and raw material without departing from technical solution of the present invention content, carry out
Any simple modification, equivalent change and modification, within the scope of equal Genus Homo technical solution of the present invention.
Claims (3)
1. a kind of method of the integral formula SSZ-13 molecular sieve of mixed templates dry glue, which comprises the steps of:
1) by silicon source, silicon source and sodium source, mixed grinding is uniform, and control each element molar ratio is 1SiO2:0.1-0.02Al2O3:
0.01-0.06Na2O；
2) at room temperature, by water, N, N, two kinds of templates of N- trimethyl adamantane ammonium and choline chloride 2-15H in molar ratio2O:
0.005-0.05R1:0.01-0.30R2It is added sequentially in beaker；
3) solution after mixing evenly is added in the uniform solid material of grinding, using kneader, after sufficiently mediating, is squeezed
Molding obtains raw material immobilized ph gradient strip；
4) it by molding raw material immobilized ph gradient strip, is put into polytetrafluoroethylene (PTFE) pallet, is placed in the polytetrafluoroethyllining lining of a small amount of water
In autoclave, after sealing, 1~3d of crystallization at 155 DEG C -165 DEG C；
5) after being cooled to room temperature reaction kettle, through deionized water washing, drying；
6) use mass fraction 30%-50% ammonium sulfate, in 80 DEG C -90 DEG C of progress ion exchange 8 hours, dried after draining
It is dry, it is roasted 4 hours at 500 DEG C -600 DEG C, obtains monoblock type SSZ-13 molecular sieve；
Wherein reaction mass sodium source is with Na2O meter, silicon source are with Al2O3Meter, silicon source are with SiO2Meter, solvent are with H2O meter, template N, N,
N- trimethyl adamantane ammonium is with R1Meter, template choline chloride is with R2Meter, each reaction mass is according to molar ratio are as follows:
1SiO2:0.1-0.02Al2O3:0.01-0.06Na2O:2-15H2O:0.005-0.05R1:0.01-0.30R2It feeds intake,
Wherein R1For N, N, N- trimethyl adamantane ammonium, R2For choline chloride.
2. according to the method described in claim 1, it is characterized in that silicon source is white carbon black, silicon powder or sodium metasilicate, silicon source in step (1)
For sodium metaaluminate, aluminum sulfate or aluminium hydroxide, sodium source is sodium metaaluminate or sodium hydroxide.
3. the monoblock type SSZ-13 molecular sieve that the method according to claim 11 is prepared is in methanol oxidation alkene
Using.
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| CN110562994A (en) * | 2019-09-27 | 2019-12-13 | 浙江天地环保科技有限公司 | method for synthesizing SSZ-13 molecular sieve by converting mixed template agent dry glue and application thereof |
| CN111056560A (en) * | 2019-11-26 | 2020-04-24 | 上海工程技术大学 | Economic synthesis method of ultrathin SSZ-13 molecular sieve membrane |
| CN113387369A (en) * | 2020-03-12 | 2021-09-14 | 瑞科稀土冶金及功能材料国家工程研究中心有限公司 | Preparation method of Cu-SSZ-13 molecular sieve |
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| CN108529642A (en) * | 2018-05-24 | 2018-09-14 | 山东泓泰恒瑞新材料有限公司 | A kind of preparation method of Cu-SSZ-13 molecular sieves |
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| CN108529642A (en) * | 2018-05-24 | 2018-09-14 | 山东泓泰恒瑞新材料有限公司 | A kind of preparation method of Cu-SSZ-13 molecular sieves |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110562994A (en) * | 2019-09-27 | 2019-12-13 | 浙江天地环保科技有限公司 | method for synthesizing SSZ-13 molecular sieve by converting mixed template agent dry glue and application thereof |
| CN111056560A (en) * | 2019-11-26 | 2020-04-24 | 上海工程技术大学 | Economic synthesis method of ultrathin SSZ-13 molecular sieve membrane |
| CN111056560B (en) * | 2019-11-26 | 2023-03-31 | 上海工程技术大学 | Economic synthesis method of ultrathin SSZ-13 molecular sieve membrane |
| CN113387369A (en) * | 2020-03-12 | 2021-09-14 | 瑞科稀土冶金及功能材料国家工程研究中心有限公司 | Preparation method of Cu-SSZ-13 molecular sieve |
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